1. Field of the Invention
This invention relates to crystallizable copolymers of propylene and to a process for producing the same.
2. Description of the Related Art
Propylene polymers exhibit a wide variety of commercial utility because of their excellent mechanical properties and optical properties. For example, propylene homopolymers have excellent rigidity, surface hardness, heat resistance, glossiness and transparency, and hence are used for various industrial parts, containers, films and non-woven fabrics. In addition, propylene/ethylene random copolymers containing small amounts of ethylene units exhibit excellent transparency, rigidity, surface hardness, heat resistance and heat-sealing properties, and, hence, are used for films, containers, etc. With larger concentrations of ethylene units, propylene/ethylene random copolymers exhibit elastomeric properties and show excellent impact absorption, heat resistance and heat-sealing properties, and, hence, are used in films as well as modifiers for thermoplastic resins.
For example, U.S. Pat. No. 5,504,172 discloses a propylene elastomer comprising 50 to 95% by mol of propylene units and 5 to 50% by mol ethylene units. The elastomer is prepared using a bridged indenyl transition metal catalyst in which each indenyl group is substituted at the 4 and 7 positions by a C2 to C20 alkyl group and is bridged by a divalent hydrocarbyl or silyl group.
Further, U.S. Pat. No. 6,525,157 discloses a propylene copolymer comprising 95 to 75% by weight of propylene-derived units and 5 to 25% by weight of ethylene-derived units, the copolymer having (a) a melting point of less than 90° C.; (b) a relationship of elasticity to 500% tensile modulus such thatElasticity≦0.935M+12,where elasticity is in percent and M is the 500% tensile modulus in MPa; and (c) a relationship of flexural modulus to 500% tensile modulus such thatFlexural Modulus≦4.2e0.27M+50,where flexural modulus is in MPa and M is the 500% tensile modulus in MPa. The copolymer is produced using a bridged indenyl transition metal catalyst, such as μ-(CH3)2Si(indenyl)2M(Cl)2, where M is Zr, Hf or Ti.
In addition to copolymers with ethylene, copolymers of propylene with higher alpha-olefins have also been extensively studied and have been found to exhibit useful properties. For example, in an article entitled “Synthesis and properties coming from the copolymerization of propene with α-olefins using different metallocene catalysts,” polymer, 46, 1567-1574 (2005), Quijada et al. report on studies of the copolymerization of propene with 1-hexene and 1-octadiene using a variety of iso- and syndioselective metallocene catalysts. Noted in this article is the tendency for the crystallinity of the copolymer to decrease with the degree of incorporation of the higher alpha-olefin, which results in a lower Tg material and hence an increase in the low temperature impact properties of the product.
For elastomeric applications, another important property in determining the impact properties of a copolymer is the weight average molecular weight of the copolymer, with higher molecular weight copolymers generally being preferred. However, with many of the metallocene catalysts used to produce copolymers of propylene with higher alpha-olefins, the generation of 1,3 insertion errors during the polymerization process tends to limit chain propagation. As a result, most existing processes for producing propylene/higher alpha-olefin copolymers result in relatively low molecular weight materials. Whereas these materials often provide excellent properties for use in adhesive applications, their low molecular weight may limit their utility as elastomers.
In accordance with the present invention, a novel product and process has now been developed in which the incorporation of small quantities (up to 30 mol %) of ethylene-derived units in a propylene/C4 to C10 alpha-olefin copolymer allows the production of a propylene terpolymer with high molecular weight and some isotactic crystallinity at high catalyst efficiency. The resultant terpolymer has less than one 1,3 insertion error per 1000 carbon atoms (as indicated by the substantial absence of any peak in the vicinity of 27.5 ppm in the 13C-NMR spectrum of the polymer) and exhibits excellent properties for use as an elastomer.
U.S. Pat. No. 6,388,040 discloses a propylene/ethylene/α-olefin terpolymer characterized in that i) there is from 0.01 mol % to less than 15 mol % of a comonomer unit with a molar ratio of ethylene units/C4-C20 α-olefin units being in the range of from 6.5×10−4 to 0.99, and from more than 85 mol % to not more than 99.99 mol % of a propylene unit with 2,1- and 1,3-propylene units being in the range of from 0 to 1 mol %, in a polymer chain determined by 13C-NMR spectroscopy; ii) a weight average molecular weight (Mw) determined by GPC is in the range of from 40,000 to 1,000,000; and iii) the amount of the component eluted in o-dichlorobenzene at a temperature of not higher than 40° C. is not more than 10% by weight based on the total weight of the terpolymer and the amount of the component eluted in o-dichlorobenzene within the +10° C. range of an elution peak temperature is not less than 75% by weight based on the weight of the component eluted at a temperature of higher than 0° C. The terpolymer is produced using a supported catalyst comprising bridged dicyclopentadienyl compound and typically has a melting point (Tm) ranging from 100° C. to 160° C.
U.S. Pat. No. 6,552,149 discloses a film-making terpolymer of propylene, comprising a mixture of different propylene terpolymer compositions and further comprising comonomer units derived from ethylene and at least one C4 to C8 alpha-olefin, the weight ratio of ethylene to the C4 to C8 alpha-olefin(s) being less than 0.3 and the hexane solubles fraction being less than 6.5% calculated from the total weight of the terpolymer. The terpolymer can be produced using a bridged metallocene catalyst and can contain from 1 to 10 wt % of ethylene and from 5 to 25 wt % of other alpha-olefins although, for the preparation of films and similar articles, the terpolymer preferably contains 0.3 to 3 wt % of ethylene-derived units and 1 to 15 wt % of the units derived from other alpha-olefins.
U.S. Pat. No. 6,627,723 discloses an adhesive poly-alpha olefin interpolymer comprising components: (A) from 60 to 94 mol % of units derived from one alpha mono-olefin having from 3 to 6 carbon atoms; (B) from 6 to 40 mol % of units derived from one or more other mono-olefins having from 4 to 10 carbon atoms and at least one carbon atom more than (A); and (C) optionally from 0 to 10 mol % of units derived from another copolymerizable unsaturated hydrocarbon, different from components (A) and (B), such as ethylene; wherein (i) the diad distribution of component (A) in the interpolymer as determined by 13C NMR divided by the calculated Bernoullian diad distribution is less than 1.07; and (ii) the storage modulus G′ of the interpolymer determined on cooling, measured at 1 Hz, intersects 3×105 Pa at an intersection temperature of less than 85° C. The interpolymer has a weight average molecular weight as determined by GPC of less than 120,000, preferably less than 90,000, and a heat of fusion of 5 to 40 J/g as determined by DSC and is useful as an adhesive.
Japanese Patent Application Publication No 9-012635 discloses a propylene/1-butene/ethylene elastomer, which is alleged to have excellent transparency, rigidity and heat sealability, and which comprises 50-85 mol % units derived from propylene, 5-50 mol % units derived from 1-butene and 10-40 mol % units derived from ethylene, wherein (1) the amount of the units derived from 1-butene is larger than that of the units derived from ethylene, (2) the intrinsic viscosity as measured in decalin at 135° C. is 0.1-12 dl/g, and (3) the molecular weight distribution (Mw/Mn) as determined by gel permeation chromatography (GPC) is 3 or below. The elastomer is produced by using a catalyst containing a metallocene compound.
European Patent Publication No. EP 1 614 699 A1 discloses a propylene elastomer comprising (a) 50 to 85 mol % units derived from propylene, (b) 5 to 25 mol % units derived from 1-butene and (c) 10 to 25 mol % units derived from ethylene, and having a molar ratio of propylene content to ethylene content of from 89/11 to 70/30 and a modulus in tension (YM), as measured in accordance with JIS 6301, of not more than 40 MPa.